U.S. patent number 4,880,851 [Application Number 07/160,802] was granted by the patent office on 1989-11-14 for aromatic composition and method for the production of the same.
Invention is credited to Tohru Yamamoto.
United States Patent |
4,880,851 |
Yamamoto |
November 14, 1989 |
Aromatic composition and method for the production of the same
Abstract
An aromatic composition comprises aromatic substances that are
encapsulated and/or clathrated in a matrix of polymer. The includes
an inorganic polymer produced from metal alkoxides; a conjugated
polymer produced from metal alkoxides and silane coupling agents;
and a conjugated polymer produced from metal alkoxides, silane
coupling agents, and organic monomers. The aromatic composition has
slow-release characteristics, so that the aromatic substances are
released over a long period of time. In a method for the production
of the aromatic composition, a catalyst for sol-gel methods that
comprises an acid or its anhydride and an organic base, and if
necessary, irradiation with ultraviolet light and/or an electron
beam are used for making the polymer.
Inventors: |
Yamamoto; Tohru (Yasu-gun,
Shiga-ken, JP) |
Family
ID: |
27291648 |
Appl.
No.: |
07/160,802 |
Filed: |
February 26, 1988 |
Foreign Application Priority Data
|
|
|
|
|
Feb 26, 1987 [JP] |
|
|
62-43718 |
Feb 27, 1987 [JP] |
|
|
62-45462 |
Apr 2, 1987 [JP] |
|
|
62-82279 |
|
Current U.S.
Class: |
523/102; 524/800;
264/4.7; 428/402.21; 512/4; 427/213.34; 428/402.24; 524/700;
524/837 |
Current CPC
Class: |
A61K
8/042 (20130101); A61K 8/11 (20130101); A61K
8/89 (20130101); A61L 9/042 (20130101); A61Q
13/00 (20130101); B01J 13/02 (20130101); C08G
77/02 (20130101); C08G 77/22 (20130101); D06M
13/005 (20130101); D06M 13/513 (20130101); D06M
16/00 (20130101); A61K 2800/57 (20130101); Y10S
514/944 (20130101); Y10S 524/916 (20130101); Y10S
522/913 (20130101); A61Q 15/00 (20130101); Y10T
428/31989 (20150401); Y10T 428/2985 (20150115); Y10T
428/2989 (20150115) |
Current International
Class: |
A61L
9/04 (20060101); B01J 13/02 (20060101); C08G
77/00 (20060101); C08G 77/02 (20060101); C08G
77/22 (20060101); B01D 013/02 () |
Field of
Search: |
;523/102 ;428/402.21
;512/4 ;264/4.7 ;524/700,800,837 ;427/213.34 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
369168 |
|
Jun 1958 |
|
JP |
|
54-6251 |
|
Mar 1979 |
|
JP |
|
22063 |
|
Feb 1983 |
|
JP |
|
135240 |
|
Aug 1984 |
|
JP |
|
5755 |
|
Jan 1988 |
|
JP |
|
Primary Examiner: Bleutge; John C.
Assistant Examiner: Woodward; David W.
Attorney, Agent or Firm: Irell & Manella
Claims
What is claimed is:
1. A method for the production of a composition having perfume
substances encapsulated or clathrated in a matrix of polymer
produced from alkoxides of metal, silicon or phosphorus, which
method comprises the steps of:
adding an acid catalyst for sol-gel methods to an aqueous mixture
of alkoxides of metal, silicon, or phosphorus, and perfume
substances so as to cause the hydrolysis of said alkoxides; and
adding a base catalyst for sol-gel methods to the reaction mixture
so as to cause the polycondensation of the hydrolysate to form a
polymer, thereby said perfume substances being encapsulated or
clathrated in the matrix of said polymer, wherein said base
catalyst is selected from the group consisting of
N,N-dimethylbenzylamine, tributylamine, tri-n-propylamine,
tripentylamine, tripropargylamine, N,N,N-trimethylethylenediamine,
and tri-n-hexylamine.
2. A method for the production of a perfume composition according
to claim 1, wherein said alkoxide is at least one selected from the
group consisting of Si(OC.sub.2 H.sub.5).sub.4, Al(O-iso-C.sub.3
H.sub.7).sub.3, Ti(O-iso-C.sub.3 H.sub.7).sub.3, Zr(O-t-C.sub.4
H.sub.9).sub.4, Zr(O-n-C.sub.4 H.sub.9).sub.4, Ca(OC.sub.2
H.sub.5).sub.2, Fe(OC.sub.2 H.sub.5).sub.3, V(O-iso-C.sub.3
H.sub.7).sub.4, Sn(O-t-C.sub.4 H.sub.9).sub.4, Li(OC.sub.2
H.sub.5).sub.2, Be(OC.sub.2 H.sub.5).sub.3, P(OC.sub.2
H.sub.5).sub.2, and P(OCH.sub.3).sub.3.
3. A method for the production of a perfume composition according
to claim 1, wherein said perfume substances have at least one major
ingredient selected from the group consisting of natural perfume of
animal or plant origin and synthetic perfumes.
4. A method for the production of a perfume composition according
to claim 1, wherein said acid and base catalyst for sol-gel methods
are added in amounts of 0.01 mol or more for every mole of said
alkoxides, respectively.
5. A method for the production of a perfume composition according
to claim 1, wherein said aqueous mixture comprises metal alkoxide,
silicon alkoxide, or phosphorus alkoxide and water in a ratio of
about 1:1 (moles alkoxide:moles water) to about 1:30 (moles
alkoxide:moles water).
Description
BACKGROUND OF THE INVENTION
1. Field of the invention
This invention relates to an aromatic composition and to a method
for its manufacture; in particular, it relates to an aromatic
composition that contains aromatic molecules that are encapsulated
and/or clathrated, giving continuous aromaticity, and to a method
for its manufacture.
2. Description of the prior art
In recent years, perfume (aromatic substances) have been mixed with
paints or printing ink so as to lend aromaticity to the coatings of
said paints and printing inks. Usually, paints, printing inks, and
the like are obtained by dissolving a resin component such as oil,
natural resins, synthetic resins, etc., into a solvent, followed by
the addition of pigments and dispersants to the solution. For
example, to these paints and printing inks, perfumes are added to
produce perfumed paint or ink. After the paint (or ink) is coated,
the resulting coated layer is heated or dried naturally in the air
so that the solvent volatilizes, resulting in the adherence of the
resin component that contains perfume. In the method mentioned
above, since the perfume is simply mixed with the paint or printing
ink, transitory aromaticity can be obtained, but the perfume
volatilizes together with the solvent, and long-term aromaticity
cannot be maintained. In particular, if the coated layer is heated,
the aromaticity is readily lost.
To solve this problem, the microencapsulation of perfumes has been
tried. For example, by the coacervation method, molecules of a
perfume are covered with a film of gelatin, polyvinyl alcohol
(PVA), or the like, resulting in microencapsulated perfume
particles with the diameter of 10-100 .mu.m. Such microencapsulated
perfumes are already commercially available. However, the perfume
inside the microcapsule is sealed tight with the film of gelatin or
PVA, and thus the scent is not released in the condition in which
the microcapsules are manufactured. If the film of the capsule is
physically destroyed, the scent is released for the first time.
When the capsule is broken open, the perfume is released once, and
the released perfume volatilizes in a short time. That is, after
microcapsules are broken open, the aroma is not maintained for a
long time.
SUMMARY OF THE INVENTION
The aromatic composition and the method for producing the same,
which are provided by this invention, overcome the problems
mentioned above of the conventional compositions and methods.
The aromatic composition of this invention comprises aromatic
substances that are encapsulated and/or clathrated in a matrix of
inorganic polymer produced from metal alkoxides.
Another aromatic composition of this invention comprises aromatic
substances that are encapsulated and/or clathrated in a matrix of
conjugated polymer produced from metal alkoxides and silane
coupling agents.
Still another aromatic composition of this invention comprises
aromatic substances that are encapsulated and/or clathrated in a
matrix of conjugated polymer produced from metal alkoxides, organic
monomers, and silane coupling agents.
The present invention provides a method for the production of an
aromatic composition comprising aromatic substances that are
encapsulated and/or clathrated in a matrix of inorganic polymers,
which method comprises the steps of: adding an acid catalyst for
sol-gel methods to a solution-containing water or a dispersion
containing water of metal alkoxides and aromatic substances so as
to cause the hydrolysis of said metal alkoxides; and adding a base
catalyst for sol-gel methods to the reaction mixture so as to cause
the polycondensation of the hydrolysate to form an inorganic
polymer, said aromatic substances being encapsulated and/or
clathrated in the matrix of said inorganic polymer thereby.
The present invention also provides a method for the production of
an aromatic composition comprising aromatic substances that are
encapsulated and/or clathrated in a matrix of conjugated polymers,
which method comprises the steps of: adding an acid catalyst for
sol-gel methods to a solution-containing water or a dispersion
containing water of metal alkoxides, silane coupling agents, and
aromatic substances so as to cause the hydrolysis of said metal
alkoxides and said silane coupling agents; adding a base catalyst
for sol-gel methods to the reaction mixture so as to cause the
polycondensation of the hydrolysate to form a conjugate polymer,
said aromatic substances being encapsulated and/or clathrated in
the matrix of said conjugate polymer thereby.
The present invention also provides a method for the production of
an aromatic composition comprising aromatic substances that are
encapsulated and/or clathrated in a matrix of conjugated polymers,
which method comprises the steps of: adding an acid catalyst for
sol-gel methods to a solution-containing water or a dispersion
containing water of metal alkoxides, silane coupling agents, and
aromatic substances so as to cause the hydrolysis of said metal
alkoxides and said silane coupling agents; adding organic monomers
to the reaction mixture; adding a base catalyst for sol-gel methods
to said reaction mixture, and immediately thereafter irradiating
the reaction mixture with at least one of these two, ultraviolet
light and an electron beam, so that the polycondensation of the
hydrolysate occurs with the polymerization of said organic monomers
and the hydrolysate of said silane coupling agents to form a
conjugated polymer, said aromatic substances being encapsulated
and/or clathrated in the matrix of said conjugated polymer
thereby.
Thus, the invention described herein makes possible the objectives
of (1) providing an aromatic composition in which the aromatic
substances are encapsulated and/or clathrated in a matrix of
inorganic or conjugated polymer, perfume molecules being released
gradually over a long period of time; (2) providing an aromatic
composition the aromaticity of which can be released slowly, which
composition can be used in the production of, for example,
furniture, clothing, cosmetics, building materials, and magnetic
cards such as prepaid cards for use in telephoning by being mixed
with printing ink, paint, printing materials for clothing, or the
like; (3) providing a slow-release composition that has deodorant
or insecticidal effects over a long period, which composition is
produced by the encapsulation and/or clathration of deodorants,
insecticides, or the like in the polymer mentioned above; and (4)
providing a method for the production of superior aromatic
compositions and slow-release compositions, both of which are
mentioned above.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
On the basis of the inventor's knowledge that if it is possible to
encapsulate or clathrate perfume molecules inside a porous polymer
matrix, an aromatic composition with excellent slow release can be
obtained, the inventor completed this invention with regard to an
aromatic composition with the use of polymers and a method for
producing the same.
The perfume used for the composition of this invention can be
natural perfumes of animal origin or plant origin, or synthetic
perfumes. The perfume is used in the proportion of 1-300 parts by
weight, and preferably 50-200 parts by weight, for every 100 parts
by weight of the metal alkoxides mentioned below. If less than 1
part by weight is used, an aromatic composition of the desired
aromaticity cannot be obtained. If more than 300 parts by weight is
used, it is difficult to encapsulate the perfume in microcapsules
or in polymer matrix.
The metal alkoxides used in the composition of this invention can
be obtained by adding methanol, ethanol, isopropanol, and other
well-known alcohols to metal oxides such as alumina, silica,
titanium (IV) oxide, and zirconium(IV) oxide. For example,
Si(OC.sub.2 H.sub.5).sub.4, Al(O-iso-C.sub.3 H.sub.7).sub.3,
Ti(O-iso-C.sub.3 H.sub.7).sub.4, Zr(O-t-C.sub.4 H.sub.9).sub.4,
Zr(O-n-C.sub.4 H.sub.9).sub.4, Ca(OC.sub.2 H.sub.5).sub.2,
Fe(OC.sub.2 H.sub.5).sub.3, V(O-iso-C.sub.3 H.sub.7).sub.4,
Sn(O-t-C.sub.4 H.sub.9).sub.4, Li(OC.sub.2 H.sub.5), Be(OC.sub.2
H.sub.5).sub.3, V(O-iso-C.sub.3 H.sub.7).sub.4, P(OC.sub.2
H.sub.5).sub.3, and P(OCH.sub.3).sub.3 can be used.
The silane coupling agent used for the composition of this
invention can be any of the wellknown silane coupling agents, such
as (.gamma.-glycidoxypropyl)trimethoxysilane,
(.gamma.-glycidoxypropyl)-methyldiethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
vinyltrimethoxysilane, vinyltrichlorosilane,
vinyltris(.beta.-methoxyethoxy)silane, vinyltriacetoxysilane,
(.gamma.-methacryloxypropyl)trimethoxysilane,
N-.beta.-(N-vinylbenzylaminoethyl)-.gamma.-
aminopropyltrimethoxysilane.hydrochloride,
.gamma.-aminopropyltriethoxysilane,
N-phenyl-.gamma.-aminopropyltrimethoxysilane,
.gamma.-(2-aminoethyl)aminopropyltrimethoxysilane,
.gamma.-(2-aminoethyl)aminopropylmethyldimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane,
methyltriethoxysilane, hexamethyldisilazane,
.gamma.-anilinopropyltrimethoxysilane,
.gamma.-chloropropyltrimethoxysilane,
.gamma.-chloropropylmethyldimethoxysilane, methyltrichlorosilane,
dimethyldichlorosilane, trimethylchlorosilane,
octadecyldimethyl[3-(trimethoxysylil)propyl]ammoniumchloride, a
mixture of aminosilanes, etc. For every 100 parts by weight of the
metal alkoxide mentioned above, 300 parts by weight or less of the
silane coupling agent can be used, with preferably 1-300 parts by
weight, and still more preferable limits of 10-40 parts by weight.
If more than 300 parts by weight is used, the polymer obtained is
not very different from that obtained with less, and is
expensive.
As organic monomers, there are acrylic acid, metharylic acid,
dimethylformamide, acrylonitrile, stylene, methyl acrylate, ethyl
acrylate, methyl methacrylate, ethyl methacrylate, etc. However,
any vinyl-type monomer, and not just those listed here, can be
used.
This kind or organic monomer is used within the limits of 200 parts
by weight or less for every 100 parts by weight of the metal
alkoxide mentioned above, and preferably 10-300 parts by weight,
with still more preferable limits of 30-100 parts by weight.
The catalyst for sol-gel method (which is used to catalyze
hydrolysis and polycondensation reactions for the metal alkoxides
and silane coupling agents mentioned above) include acids, their
anhydrides, and organic bases. Thes organic bases are tertiary
amines that are substantially insoluble in water and soluble in
organic solvents.
As the acid used as a catalyst, it is possible to use mineral acid
such as hydrochloric acid, sulfuric acid, nitric acid, etc. It is
possible to obtain the same effects with the use of the anhydride
of mineral acids, for example, with hydrogen chloride gas. Also,
organic acids and their anhydrides can be used. For example,
tartaric acid, phthalic acid, maleic acid, dodecylsuccinic acid,
hexahydrophthalic acid, methyl endic acid, pyromellitic acid,
benzophenonetetracarboxylic acid, dichlorosuccinic acid, chlorendic
acid, phthalic anhydride, maleic anhydride, dodecylsuccinic
anhydride, hexahydrophthalic anhydride, methyl endic anhydride,
pyromellitic dianhydride, benzophenonetetracarboxylic anhydride,
dichlorosuccinic anhydride, and chlorendic anhydride can be used.
Per mole of the metal alkoxide, 0.01 mol or more of these acids,
and preferably 0.01-0.5 mol, can be used. If the amount of the acid
is less than 0.01 mol, the hydrolysis of the metal alkoxides does
not proceed substantially.
As such tertiary amines used as a catalyst,
N,N-dimethylbenzylamine, tributylamine, tri-n-propylamine,
tripentylamine, tripropargylamine, N,N,N-trimethylethylenediamine,
tri-n-hexylamine, etc., can be used. The tertiary amine can be used
at equimolar amounts or in excess amounts of the acid mentioned
above; preferably, it is used in amounts ranging from 0.01 to 0.06
mol per mole of the metal alkoxide. The amount of tertiary amine to
be used can be chosen within the limits mentioned above with
consideration of its degree of dissociation. If there is too little
tertiary amine, then after the hydrolysis of the metal alkoxide,
the rate of polycondensation is greatly slowed.
As the solvent that can be used in the method, in addition to the
water used in the hydrolysis, it is possible to use an organic
solvent. As the organic solvent, solvents that are miscible with
water or solvents that can be partly dissolved in water can be
used. These include, for example, methanol, ethanol, butanol,
n-propanol, isopropanol, pentanol, hexanol, acetone, methyl ethyl
ketone, and formamide.
The aromatic composition of this invention is manufactured by the
following three main methods. In the first method, a polymer is
made by the use of a metal alkoxide, and the perfume is trapped in
a matrix of this polymer. In the second method, a polymer is made
by the use of a metal alkoxide and a silane coupling agents, and
the perfume is trapped in a matrix of this polymer. In the third
method, a polymer is made by the use of a metal alkoxide, silane
coupling agent, and organic monomer, and the perfume is trapped in
a matrix of this polymer.
In the first method, for example, the metal alkoxide mentioned
above is dissolved in the organic solvent mentioned above, such as,
for example, alcohol. The concentration of the metal alkoxide is
not set within any particular limits, but ordinarily, it is 500-600
g/l. Next, water is added to the metal alkoxide solution. The
amount of water that is added is at the proportion of 1-30 moles
per mole of the metal alkoxide. The water can be mixed beforehand
with the alcohol mentioned above. To this solution of metal
alkoxide (including water), the perfume mentioned above is added to
obtain a solution or dispersion. The perfume can be added, for
example, in the form of a solution in organic solvent or aqueous
solution. To this, an acid (or its anhydride) catalyst for the
sol-gel method mentioned above is added and the mixture is mixed at
room temperature. The reaction is carried out at room temperature
to prevent the volatilization of the perfume. With this treatment,
hydrolysis is virtually complete. Into this reaction mixture, the
tertiary amine catalyst (the other of the two forms of the
catalyst) is added. When the tertiary amine is added, a
polycondensation reaction proceeds and gelatin is completed within
a relatively short time. The time taken for gelation or degree of
gelation depends on the amount of water used and the amount of
catalyst for the sol-gel method that is used. In general, it is
possible to control the time of gelation from about 2 seconds to
several dozens of minutes.
The gel mentioned above is constituted by an inorganic polymer
formed by the hydrolysis and polycondensation of the metal alkoxide
mentioned above. Perfume particles (i.e., fine granules of solid or
liquid comprising molecules of perfume, and as the case may be, the
organic solvent that containes the molecules of perfume) are
trapped in a matrix of this polymer. More particularly, it is
possible to encapsulate and/or clathrate particles of perfume in
the following kind of form. In the reaction mentioned above, the
metal alkoxide undergoes hydrolysis and polycondensation, including
a cross-linking reaction, resulting in fine particles with a
three-dimensional structure. When the particles with a
three-dimensional structure is formed, the particles of perfume are
trapped into the three-dimensional network constituted by the said
structure. As a result, the particles of perfume are encapsulated
in particles of polymer. These polymer particles gather in a number
of clumps, and they further undergo polycondensation and
cross-linking reactions to form a continuous three-dimensional
matrix. THe perfume particles are taken into the space inside, so
as to be encapsulated or clathrated. When the solvent including
alcohol produced by the polycondensation reaction is removed by
volatilization from the three-dimensional matrix, as will be
described below, the perfume remains in the porous matrix
framework. It is known that the pores of the porous matrix
mentioned above have an extremely small diameter (Science, Vol. 79,
192 (1986); Nikkei Science Inc.). For that reason, the perfume
volatilizes gradually, which results in the fragrance continuing
long-term.
In the second method, a silane coupling agent is used in addition
to the metal alkoxide of the first method described above. For
example, first, to a solution that contains metal alkoxide in
alcohol and water, perfume, silane coupling agent, and a
light-sensitizer, if needed, are added. As the light-sensitizer,
diacetyl and the like can be used. The light-sensitizer accelerates
the photocondensation reaction brought about by the ultraviolet
radiation. Moreover, if needed, other monomers and polymers can be
added. As such monomers, there are vinyl-type monomers, and as the
polymers, there are copolymers and polymers polymerized from vinyl
chloride, vinyl acetate, butadiene, etc. These monomers and
polymers are added for the purpose of acceleration of the
polymerization and copolymerization reactions described below, and
for the purpose of the formation of a homogeneous and strong
polymer.
To this mixture, as in the first method described above, a catalyst
for the sol-gel methods is added, and the mixture is irradiated as
needed by ultraviolet light and/or by an electron beam. The
wavelength of the ultraviolet light is 250 nm or less. If this
wavelength is more than 250 nm, the radical polymerization,
cross-linking reaction, and polycondensation reaction mentioned
below will probably not proceed sufficiently. The dose of radiation
with an electron beam can be within the limits of 0.1-50 megarads.
The amount of energy is preferably 150-200 kV. If less than 0.1
megarad is used, the radical polymerization, cross-linking
reaction, and polycondensation reaction mentioned below will
probably not proceed sufficiently. There is no need for more than
50 megarads. The radiation equipment for the electron beam can be,
for example, an area beam electronic radiation device such as the
Curetron (Nisshin Denki Co.).
The metal alkoxide and silane coupling agent in the reaction
mixture mentioned above are hydrolyzed, followed by the subsequent
polycondensation reaction, which proceeds rapidly. Moreover, when
the silane coupling agent contains, for example, an epoxy moiety,
the acid and base catalyst mentioned above cause cleavage of the
epoxy ring, and ring-opening polymerization occurs. When a reaction
mixture is irradiated with ultraviolet light and/or an electron
beam, radicals arise from vinyl groups, and these radicals cause
the cross-linking reaction and radical polymerization (i.e.,
photopolymerization or electronbeam polymerization) of the organic
portion of the silane coupling agent. When ultraviolet light is
used for radiation, the radicals arise from the light-sensitizer.
In addition to an electron beam and ultraviolet light, other kinds
of radiation can be used.
In these ways, the hydrolysis and polycondensation of the metal
alkoxide and the inorganic portion of the silane coupling agent are
made to proceed rapidly. Radical polymerization (including
cross-linking polymerization) of the organic portion of the silane
coupling agent can also be made to proceed rapidly. The reactions
mentioned above occur between the silane coupling agents, between
the metal alkoxides, and/or between the silane coupling agent and
the metal alkoxide. The inorganic portion of the silane coupling
agent (i.e., the silica portion) is taken into the framework of
inorganic polymer molecules produced from the hydrolysate of the
metal alkoxide, or forms an inorganic polymer by polycondensation
arising among the silane coupling agents. The organic portion of
the silane coupling agent that is attached to the silicon atom
forms a cross-linked moiety with an organic portion of the other
silane coupling agent molecule.
The polymer formed in this way has an inorganic polymer portion
formed from the hydrolysis and polycondensation of the metal
alkoxide and the silane coupling agent and also an organic polymer
portion formed by the polymerization of the polymerizable group
(i.e., organic portion) of the silane coupling agent. In other
words, the metal alkoxide and the silane coupling agent react to
form a polymer in which the metal alkoxide and the silane coupling
agent are bound on the molecular level (this can be thought of as a
conjugated polymer with an organic portion and an inorganic
portion). The reaction system containing the said polymer becomes a
gel, as in the first method mentioned above. The conjugated polymer
forms a matrix with a three-dimensional structure that is almost
the same structure as in the first method, and the perfume
particles that are present in the reaction system are encapsulated
or clathrated in the polymer matrix almost in the same way as in
the first method.
In the third method, in addition to the metal alkoxide and silane
coupling agents used in the second method mentioned above, an
organic monomer is used. For example, first, to a solution of metal
alkoxide in water and alcohol, perfume and silane coupling agent
are added. To the mixture, an acid catalyst for sol-gel methods is
added so as to hydrolyze the metal alkoxide, followed by the
addition of the organic monomer. When photocondensation is carried
out by the use of ultraviolet light, a light-sensitizer such as
diacetyl can be added. Furthermore, other monomers and polymers can
be added as in the second method, if needed. To this mixture, a
base catalyst for sol-gel methods is added, and the mixture is
irradiated with ultraviolet light and/or an electron beam. The
reaction that is brought about in this way is similar to the
reaction in the second method, and polymerization of organic
monomers by a radical reaction occurs. This polymerization can
occur between molecules of the organic monomer, and also between
molecules of the said organic monomer and the organic portion
(e.g., the epoxy moiety, vinyl moiety, etc.) of the silane coupling
agent. In this way, a conjugated polymer is produced that has more
organic portions than those of the polymer of the second method,
and that has a complicated cross-linked structure. The perfume
particles are encapsulated and/or clathrated in the conjugated
polymer matrix as in the first and second methods described
above.
In general, as a catalyst for sol-gel methods, mineral acids are
widely known, but if such catalysts are used in the third method,
compared to the polymerization of organic monomers, the hydrolysis
and polycondensation reactions of the metal alkoxides and silane
coupling agent become extremely slow. As a result, a homogeneous
conjugated polymer is not formed. On the contrary, in this
invention, catalysts for sol-gel methods mentioned above that has
been developed by the inventors are used, and the reaction is very
much accelerated, so that an homogeneous conjugated polymer is
formed.
When an electron beam and/or ultraviolet light is used for radical
polymerization in the second and third methods described above, the
reaction proceeds at low temperatures such as 20.degree.-30.degree.
C. so that the perfume will not volatilize and be lost. With the
composition obtained by the use of the first and second methods,
when the solvent and the alcohol are removed from the reaction
system (including the framework of the matrix), a porous polymer
matrix including perfume particles can be obtained. For that
reason, with this composition as well, the slow release of the
perfume is very satisfactory. The conjugated polymer in the
composition obtained by these methods includes an organic portion
in the molecule, so the rate of film formation, mechanical
strength, processability, and adhesion to various kinds of base
materials are excellent. For that reason, by application to base
materials such as wood, synthetic resin, metals, fabrics, non-woven
cloth, etc. with a paint to which this composition is added,
various kinds of products with aromaticity having excellent slow
release properties and with excellent durability can be
obtained.
In general, the reaction mixtures that contain perfume particles
that are encapsulated or clathrated by the first, second, and third
methods described above are gels. The reaction mixture may be a sol
that contains fine polymer particles, and the sol may also be used
for various purposes. When the gel is mashed, for example, it can
be mixed with printing ink or paint to give ink or paint with
aromaticity. Alternatively, the gel can be dried, to give a porous
polymer that contains perfume, and this can be mixed with paints
and the like. This kind of ink and paint can be applied to fabric
goods, building materials, furniture, etc., or these articles can
be soaked in it. It is also possible to include this in cosmetics.
In place of the perfume, insecticides or deodorants can be
encapsulated and/or clathrated to give them longlasting effects.
The various products on which the composition of this invention is
used can maintain their aromaticity, insecticidal properties, or
deodorant effects long-term.
______________________________________ Example 1 Components Amounts
(molar ratio) ______________________________________ Ethyl silicate
25 g (1) Water 8.6 g (4) Ethanol 25 ml Aldehyde-type perfume 25 g
Hydrochloric acid 0.129 g.sup.(a) (0.03) N,N--Dimethylbenzylamine
0.321 g (0.02) ______________________________________ NOTE:
.sup.(a) Calculated in terms of hydrogen chloride.
After the ethanol, ethyl silicate, and perfume were mixed, water
and hydrochloric acid were added, and the mixture was stirred for
several seconds. N,N-Dimethylbenzylamine was added, and the mixture
was stirred for 50 seconds more to obtain a gel. Next, the
resulting gel was mashed and then dispersed evenly in printing ink
(which contained 255 g of urethaneacrylate polymer emulsion and 7.2
g of pigment.)
The aromatic ink composition obtained was applied on the surface of
cotton cloth, and was found to have uniform aromaticity for 8
months. When printing ink that contained acrylate-polymer emulsion
instead of the urethane-acrylate polymer emulsion was used, the
same results were obtained.
______________________________________ Example 2 Components Amounts
(molar ratio) ______________________________________ Ethyl silicate
25 g (1) Water 8.6 g (4) Ethanol 25 ml (.alpha.-Glycidoxypropypl)
trimethoxysilane (Tore silicone SH6040) 6 g Aldehyde-type perfume
25 g Hydrochloric acid 0.129 g.sup.(a) (0.03)
N,N--Dimethylbenzylamine 0.162 g (0.01)
______________________________________ NOTE: .sup.(a) Calculated in
terms of hydrogen chloride.
Ethanol, ethyl silicate, perfume, silane coupling agent (Tore
silicone SH 6040), and water were mixed, and then hydrochloric acid
and N,N-dimethylbenzylamine was added in this order by the same
method as in Example 1. The resulting gel was mashed and then mixed
uniformly in an ethanol solution containing 90% of nylon 6/11. This
mixture was applied to the surface of a sheet made of polyvinyl
chloride so that it would be 20 .mu.m thick after drying. The scent
lasted for 2 months.
______________________________________ Example 3 Components Amounts
(molar ratio) ______________________________________ Ethyl silicate
25 g (1) Water 4.3 g (2) Isopropyl alcohol 20 ml Acetone 10 ml
(.alpha.-Glycidoxypropypl) trimethoxysilane (Tore silicone SH6040)
7 g Ester-type perfume 20 ml Hydrochloric acid 0.129 g.sup.(a)
(0.03) N,N--Dimethylbenzylamine 0.162 g (0.01)
______________________________________ NOTE: .sup.(a) Calculated in
terms of hydrogen chloride.
In place of ethanol, isopropyl alcohol was used, and a reaction was
carried out as in Example 2. The resulting gel was mashed and then
mixed with acetone. Cloth (100% cotton broadcloth) was soaked in
this mixture, removed, and then dried. The amount of mixture that
remained on the cloth per unit area after drying was 13.8
g/m.sup.2. This aromatic cloth remained scented for 6 months.
______________________________________ Example 4 Components Amounts
(molar ratio) ______________________________________ Ethyl silicate
25 g (1) Water 4.3 g (2) Isopropyl alcohol 25 ml Acetone 12 ml
(.alpha.-Glycidoxypropypl) trimethoxysilane (Tore silicone SH6040)
6 g Acrylonitrile 18.9 ml Ester-type perfume 10 ml Hydrochloric
acid 0.129 g.sup.(a) (0.03) N,N--Dimethylbenzylamine 0.324 g (0.02)
______________________________________ NOTE: .sup.(a) Calculated in
terms of hydrogen chloride.
Isopropyl alcohol, ethyl silicate, perfume, silane coupling agent,
acrylonitrile monomer and water were mixed, and to this,
hydrochloric acid and N,N-dimethyl-benzylamine was added in that
order by the same method used in Example 1. The gel that was
produced was mashed and diluted with acetone. The mixture was
coated on the surface of glass plate so that it would be 10 .mu.m
thick after drying. The scent lasted for 2 months.
______________________________________ Example 5 Components Amounts
(molar ratio) ______________________________________ Ethyl silicate
25 g (1) Water 8.6 g (4) Ethanol 25 ml Deodorant
(Fresh-Shuraimatsu; 50 g Shiraimatsu Inc.) Hydrochloric acid 0.129
g.sup.(a) (0.03) N,N--Dimethylbenzylamine 0.324 g (0.02)
______________________________________ NOTE: .sup.(a) Calculated in
terms of hydrogen chloride.
Ethyl silicate, ethanol, deodorant, and water were mixed, and then
hydrochloric acid and N,N-dimethylbenzylamine were added in this
order by the same method as in Example 1. The resulting gel was
mashed and then applied on the internal surface of a plastic
garbage container for use in kitchens. The deodorant effects were
retained for 2 months.
It is understood that various other modifications will be apparent
to and can be readily made by those skilled in the art without
departing from the scope and spirit of this invention. Accordingly,
it is not intended that the scope of the claims appended hereto be
limited to the description as set forth herein, but rather that the
claims be construed as encompassing all the features of patentable
novelty that reside in the present invention, including all
features that would be treated as equivalents thereof by those
skilled in the art to which this invention pertains.
* * * * *